CN109937125A - Through handling porous material - Google Patents

Through handling porous material Download PDF

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Publication number
CN109937125A
CN109937125A CN201780070222.2A CN201780070222A CN109937125A CN 109937125 A CN109937125 A CN 109937125A CN 201780070222 A CN201780070222 A CN 201780070222A CN 109937125 A CN109937125 A CN 109937125A
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China
Prior art keywords
cellulosic material
epoxy resin
case
method described
processing scheme
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CN201780070222.2A
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Chinese (zh)
Inventor
S·W·金
陈雪
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B27K3/15—Impregnating involving polymerisation including use of polymer-containing impregnating agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34—Organic impregnating agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K2240/00—Purpose of the treatment
    • B27K2240/20—Removing fungi, molds or insects
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K2240/00—Purpose of the treatment
    • B27K2240/30—Fireproofing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K2240/00—Purpose of the treatment
    • B27K2240/70—Hydrophobation treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K2240/00—Purpose of the treatment
    • B27K2240/90—UV-protection
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/54—Aqueous solutions or dispersions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C08L23/0876—Neutralised polymers, i.e. ionomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/04—Epoxynovolacs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines

Abstract

A method of be used to prepare through handle cellulosic material, it includes: provide cellulosic material；First processing scheme, it includes the cellulosic material is impregnated with the aqueous solution comprising polymer, the polymer includes water-soluble poly ether amines；With second processing scheme, it includes the cellulosic material is impregnated with modifying agent, the modifying agent includes aqueous dispersions, and the aqueous dispersions include to contain epoxy resin.

Description

Through handling porous material
Background technique
Porous material (such as cellulosic material) need to be protected against only insect infestations, rotten and immersion, to help In the physical characteristic for saving cellulosic material.One example of this kind of cellulosic material is timber.Known a variety of inorganic agents and Method for preserving can preservation cellulosic material.
Modern method for preserving is typically related to inorganic agent pressure treatment cellulosic material.Pressure treatment usually to handle Agent is penetrated into the entire porous structure of cellulosic material.Inorganic agent is usually a kind of to assign physics desired by cellulosic material Characteristic and the compound selected.For example, cellulosic material hardness is improved, increases cellulosic material water resistance and improves fine It is interesting for tieing up the inorganic agent of cellulosic material dimensional stability.Timber can absorb the 100% of up to its weight in water, So as to cause swelling of wood, this to cause wood shrinkage after losing water by evaporation.This water absorption/evaporation process It is inhomogenous and generates internal stress in wood, causes to split, warpage, arch, bending, distortion, curling etc..In addition, water energy Enough serve as the path for the organism (such as insect or fungi) for making cellulosic material degrade.It drives insect or forms fungi and reduce to Inorganic agent that is minimum or improving cellulosic material overall durability is interesting.In addition, inorganic agent can improve wind resistance Property, ultraviolet radioactive resistance, high temperature and stability under low temperature, pest resistance, fire resistance and fiber material material may be influenced Manage the other problems of characteristic.
It is expected that a kind of improved cellulosic material inorganic agent.
Summary of the invention
A method of be used to prepare through handle cellulosic material, it includes: provide cellulosic material；First processing side Case, it includes the cellulosic material is impregnated with the aqueous solution comprising polymer, the polymer includes water-soluble poly ether amines；With Second processing scheme, it includes the cellulosic material is impregnated with modifying agent, the modifying agent includes aqueous dispersions, the moisture Dispersion liquid includes to contain epoxy resin.
Specific embodiment
As used herein, term " porous material " refers to permeable material so that fluid can by means of hole or its Its channel and flow through wherein.One example of porous material is cellulosic material.Other examples of porous material include stone, mix Solidifying soil, ceramics and its derivative.As used herein, term " cellulosic material " refers to the material comprising cellulose as structural constituent Material.The example of cellulosic material includes timber, paper, textile, rope, particle board and other biologies and synthetic material.Such as this Used in text, timber includes solid wood and all Wood composite materials (for example, hardboard, engineered wood product etc.).Fiber material Material usually has the porous structure for defining multiple holes.
As used herein, unless otherwise specified, phrase " molecular weight " refers to weight average molecular weight.In certain feelings Under condition, molecular weight is measured by gel permeation chromatography (Gel permeation chromatography, GPC).
" through handling cellulosic material " is a kind of with inorganic agent processing with the cellulose of modified cellulosic materials characteristic Material.It include but is not limited to the hydrophobicity enhanced, dimensional stability, antifungal activity, anti-insect through the modified characteristic of inorganic agent Property, hardness, appearance, UV stability, fire line and coatability.Enhance fibre by drop low water absorption and evaporation rate The hydrophobicity of dimension cellulosic material can provide other ancillary benefits, such as dimensional stability, to reduce the internal stress of expansion and contraction.
" inorganic agent " is the substance for making the characteristic of cellulosic material modified when combining with cellulosic material.In a kind of situation Under, inorganic agent includes polymer and modifying agent.Inorganic agent is applied in cellulosic material.It is a kind of that inorganic agent is applied to fiber The method of cellulosic material is impregnated by using pressure treatment.In one case, polymer is applied as a part of solution It is added on cellulosic material.The known other methods for applying inorganic agent, such as brushing, coating, spraying, dip-coating, immersion and extruding. Upon application, inorganic agent will penetrate at least part hole of cellulosic material.
As used herein, polymer refers to the molecule formed by the monomer of one or more types.Polymer is preferably The mixture of copolymer or copolymer and polymer.As used herein, copolymer can refer to alternate copolymer, periodic copolymer, Statistical copolymer, random copolymer, block copolymer, graft copolymer or other copolymers as known.As used herein, Copolymer refers to the polymer formed and merging two or more monomers.The example of copolymer include bipolymer, The copolymer of terpolymer, quadripolymer and other higher orders.
In one case, polymer includes water-soluble poly ether amines.As used herein, " water solubility " means solution in water With at least polyethers-amine of 10 weight %, without mutually separating, precipitating or solid residue.In one case, polyetheramine is Polyether monoamine.In one case, polyetheramine is polyether diamine.In one case, polyetheramine is polyether monoamine and polyethers two The mixture of amine.In one case, polyetheramine of the molecular weight less than 2000 is selected.In one case, selection molecular weight is small In 1500 polyetheramine.In one case, polyetheramine of the molecular weight less than 1000 is selected.In one case, molecule is selected Measure the polyetheramine less than 500.The example for being suitable for the invention polyetheramine includes being purchased from Heng Zi Mann (Huntsman Corporation JEFFAMINES).These include all series of JEFFAMINES, including M, D, ED and EDR series produce Object.
As used herein, refer to acrylate and first using term " (methyl) " before another term of such as acrylate Base acrylate.For example, term " (methyl) acrylate " refers to acrylate or methacrylate；Term " (first Base) acrylic compounds " refer to acrylic compounds or methacrylic；And term " (methyl) acrylic acid " refers to acrylic acid or methyl Acrylic acid.
In one case, polymer is the component part of solution.In one case, solution is to include polymer and water Medium.Aqueous solution is prepared, so that the viscosity of aqueous solution is suitable for the hole of permeable fiber cellulosic material to be distributed by cellulosic material. In one case, the viscosity of solution is less than 5000cP at ambient temperature.In one case, the viscosity of solution is in environment temperature Degree is lower to be less than 500cP.In one case, solution also includes one or more additives.In one case, it is deposited in solution Any solid be held in stable suspension and in the hole that cellulosic material can be carried to by dispersion liquid.In a kind of feelings Under condition, the solid content of polymer is 1 to 50 weight %.In one case, the solid content of polymer is 15 to 45 weights Measure %.In one case, the solid content of polymer is 25 to 40 weight %.In one case, the solid of polymer contains Amount is 30 to 40 weight %.
Modifying agent is the substance that porous material characteristic is improved when being added in porous material.In one case, modified Agent is containing epoxy resin.It in one case, is epoxy resin containing epoxy resin.It in one case, is to inhale containing epoxy resin Receive the thermoplastic polymer of epoxy resin.The example of the commercially available thermoplastic polymer for absorbing epoxy resin is MaincoteTM AEH-10 (is purchased from Dow Chemical).In one case, the epoxy resin portion containing epoxy resin includes single epoxy Resin.In one case, the epoxy resin portion containing epoxy resin includes the mixture of epoxy resin.In one case, Epoxy resin portion containing epoxy resin is the diglycidyl ether of bisphenol-A, the diglycidyl ether of Bisphenol F, 1,4- butanediol Diglycidyl ether, 1,6 hexanediol diglycidylether, the 2-glycidyl ester of phthalic acid, 1,4 cyclohexane dimethanol Diglycidyl ether, 1,3- cyclohexanedimethanodiglycidyl diglycidyl ether, hexahydrophthalic acid 2-glycidyl ester or phenolic aldehyde Varnish gum, or combinations thereof.In one case, the thermoplastic portions containing epoxy resin include (methyl) acrylic latex.It is suitable The monomer for being used to prepare acrylic based emulsion includes acrylate and methacrylate, for example, methyl acrylate, ethyl acrylate, Butyl acrylate, 2-EHA, methyl methacrylate, ethyl methacrylate, butyl methacrylate and first Base 2-EHA and a combination thereof.
In one case, modifying agent is the epoxy resin dispersion liquid stable by emulsifier.Dispersion liquid is preferably moisture Dispersion liquid.Epoxy resin can be solid epoxy or liquid epoxies.In one case, dispersion liquid includes water, epoxy Resin and one or more emulsifying agents.Aqueous dispersions are preferably stable dispersion liquid.Stable dispersions are to support upon formation Resist its characteristic to change over time, and is therefore suitable for the dispersion liquid penetrated into the hole of cellulosic material.In one kind In the case of, dispersion liquid is substantially free of solvent, for example, having the solvent less than 1 volume %.In one case, aqueous dispersions With the solvent less than 0.1 volume %.In one case, dispersion liquid is free of solvent.The example of commercially available dispersion liquid includes purchase From the OUDRASperse of Dow ChemicalTM, such as OUDRASperseTM WB 3001、OUDRASperseTM4001 He of WB OUDRASperseTMWB 6001.In one case, emulsifier is surfactant.In one case, surfactant It is non-ionic or anion.In one case, surfactant is epoxy functionalized surfactant.Epoxy functionalized surface Activating agent is a kind of surfactant, contains and reacts with containing epoxy material, to become the official for solidifying the integral part of matrix It can group.In one embodiment, surfactant epihalohydrin or the processing of multifunctional (two or higher) epoxides, obtain ring Oxygen functional surface activating agent.In a preferred embodiment, at epihalohydrin or multifunctional (two or higher) epoxides Surfactant is managed, is non-ionic.The example of nonionic surfactant includes alcohol alcoxylates alkoxylated alkylphenol, alkane Oxygroup ester, alkoxylate acid esters, ethylene oxide/propylene oxide copolymer (block and random), amine alcoxylates, alkoxy Change polyalcohol and mercaptan.In one case, dispersion liquid includes the combination of epoxy functionalized surfactant.In another case, Dispersion liquid includes the combination of epoxy functionalized surfactant and another surfactant.As used herein, " EO " refers to epoxy Ethane and " PO " refers to propylene oxide.
In one case, modifying agent is the component part of aqueous dispersions.In one case, dispersion liquid is comprising being modified The medium of agent and water.Prepare aqueous dispersions make the suspended particulate size in dispersion liquid be adapted to pass through cellulosic material hole so as to It is scattered in entire cellulosic material.In one case, the solid of aqueous dispersions has the average particle size less than 50 microns.? In a kind of situation, the solid of aqueous dispersions has the average particle size less than 500nm.In one case, the solid of aqueous dispersions With the average particle size for being less than 350nm.In one case, the solid of aqueous dispersions has the average particle size less than 250nm.? In a kind of situation, the solid of aqueous dispersions has 100 to 250nm average particle size.In one case, dispersion liquid also includes one Kind or multiple additives.In one case, any solid in the presence of aqueous dispersions is held in stable suspension simultaneously And it can be carried in the hole of cellulosic material by dispersion liquid.In one case, the solid content of dispersion liquid is 0.1 to 90 weights Measure %.In one case, the solid content of dispersion liquid is 1 to 80 weight %.In one case, the solid content of dispersion liquid For 5 to 70 weight %.In one case, the solid content of dispersion liquid is 10 to 60 weight %.In one case, dispersion liquid Solid content be 12 to 50 weight %.In one case, the solid content of dispersion liquid is 15 to 40 weight %.Prepare moisture Dispersion liquid, so that the viscosity of the dispersion liquid containing epoxy is suitable for the hole of permeable fiber cellulosic material to be distributed in entire cellulosic material.? In a kind of situation, the viscosity of solution is 1cP to 5000cP at ambient temperature.In one case, the viscosity of solution is in environment At a temperature of be less than 1000cP.
In one case, the aqueous solution comprising polyetheramine is combined to allow with comprising the aqueous dispersions containing epoxy resin Porous material is handled in a single step.
It combines inorganic agent with cellulosic material.In one case, as described herein, inorganic agent is drawn by pressure treatment Enter in cellulosic material.In another case, inorganic agent is to introduce fiber material by other technologies known in fields In material, such as brushing, dip-coating, immersion, spraying and extruding.Inorganic agent becomes to immerse at least part hole of cellulosic material In, and thereby increase the weight of cellulosic material.In one case, polymer increases the weight of cellulosic material 1% to 80% (as will be calculated after cellulosic material drying).In one case, inorganic agent (polymer and modifying agent Combination) make the weight of cellulosic material increase 5% to be greater than 100% (as will cellulosic material dry after calculate).
In one case, inorganic agent includes one or more additives.Additive can be used as containing the molten of polymer A part of liquid, as modifying agent a part and including or can separately include.It is known to make through handling fiber material Material addition characteristic additive be it is suitable, such as fire retardant, dispersing agent and/or dyestuff.For example, additive can be organic Compound, metallic compound or organo-metallic compound.In one case, additive is a kind of improvement polymer to timber The material of wetting or infiltration, such as stable solvent in dispersion liquid or surfactant (anion, cation or nonionic Type).The example of additive include solvent, filler, thickener, emulsifier, dispersing agent, buffer, pigment, bleeding agent, resist it is quiet Electric agent, odoring substance, corrosion inhibitor, preservative, siliconizing medium, rheology modifier, antisettling agent, antioxidant, other crosslinkings Agent (such as dihydric alcohol and polyalcohol), optical brightener, wax, coalescent, biocide and defoaming agent.This kind of filler can Including silica, Ca (OH)2Or CaCO3.In addition, inorganic agent can be used in combination with timber preservative, the timber preservative Contain such as copper-ammonia, copper-amine, copper-ammonia-amine compound, quaternary ammonium compound or other systems.For example, inorganic agent can be with Alkaline copper-quaternary ammonium (Alkaline Copper-Quaternary ammonium；ACQ) preservative system is used together.Inorganic agent It can also be used together with the wood preservation technology of zinc salt or boron-containing compound is used.It is optionally possible to be added into inorganic agent Other additives, such as insecticide, termiticide and fungicide.In one case, additive as dispersion liquid one Part includes and formed stable suspension.In one case, one or more surface-actives are added into dispersion liquid Agent.In one case, selection reduces the surfactant that polymer is gelled at cellulosic material surface.In a kind of situation Under, selection makes the increased surfactant of the amount for the polymer being immersed in cellulosic material.For example, suitable surface is living Property agent can be nonionic, anion or cationic.The example of nonionic surfactant includes: alcohol alcoxylates, alcoxyl It is base alkyl phenol, aliphatic ester, amine and amide derivatives, alkyl polyglucoside, ethylene oxide/propylene oxide copolymer, more First alcohol and alkoxylated polyol.For example, nonionic surface active agent is purchased from Dow Chemical TERGITOLTML-62.The example of anionic surfactant includes: alkyl sulfate, alkyl ether sulfate, sulphation alkanol Amide, alhpa olefin sulfonate, lignosulfonates, sulfosuccinate, fatty acid salt and phosphate.For example, anion Type surfactant is the DOWFAX available commercially from Dow ChemicalTMC10L.The example of cationic surface active agent includes Alkyl trimethyl ammonium salt.
In one case, cellulosic material is prepared as through handling cellulosic material using pressure treatment.To pressure The pressure of processing cellulosic material can be higher or lower than atmospheric pressure.In one case, pressure is lower than environmental pressure, such as 0.0001 to 0.09MPa (0.75 arrives 675mmHg).In another case, pressure is higher than environmental pressure, such as 0.1 to 1.7MPa (750 to 12750mmHg).It is envisaged that known pressure treatment method is suitable for impregnating fiber material with inorganic agent in fields Material.The temperature of pressure treatment (such as environment temperature is to 150 DEG C) can carry out in certain temperature range.
In one case, through processing cellulosic material according at least to the first processing scheme and second processing scheme system It is standby.In one case, the first processing scheme includes to use polymer impregnated fabric cellulosic material.First processing scheme includes following step It is one or more of rapid: (a) to deposit cellulosic material in a reservoir；(b) keep container under vacuum 5 to 60 minutes； (c) polymer is introduced into container；(d) container 1.03MPa is pressurized to maintain 5 to 60 minutes；(e) excess polymeric is discharged； (f) optionally by excess polymeric and (g) is removed in vacuo that cellulosic material is 24 to 48 hours air-dried at 20 to 60 DEG C.? In a kind of situation, polymer is a part of aqueous dispersions.In one case, step (d) carries out under ambient pressure.
In one case, the product of the first processing scheme is then prepared according to second processing scheme, the second processing Scheme impregnates cellulosic material with regulator.Second processing scheme one or more of comprises the steps of: (a) making according to The cellulosic material of one processing scheme preparation deposits in a reservoir；(b) modifying agent is introduced into container；(c) container is maintained 5 to 60 minutes under vacuum or increased pressure；(d) optionally by excess agent is removed in vacuo；(e) by cellulosic material It is air-dried 24 to 48 hours at 60 DEG C.In one case, the first processing scheme and second processing scheme are combined, thus will be repaired The step of changing the first processing scheme (c) is to also comprise modifying agent.
Several drying steps can carry out under series of temperature, wherein the duration of air drying steps and temperature at than Example.Suitable air-dried temperature is between room temperature (about 20 DEG C) and 180 DEG C.Drying can in air, in nitrogen or other conjunctions It is carried out in suitable atmosphere.
It is tested using water logging, protecting association criterion E4-11 program according to american wood, (" timber through pressure treatment is refused Aqueous standard method of test (Standard Method of Testing Water Repellency of Pressure Treated Wood) ") water repellency of the measurement through processing cellulosic material.Water logging test is related to: firstly, providing comprising as herein The preparation through processing cellulosic material through handle thin slice, with comprising according to the first processing scheme described herein handle (but Wherein dispersion liquid is replaced with distilled water) cellulosic material control thin slice；Second, measurement is through processing thin slice and control thin slice two The tangential dimension of person, to obtain initial tangential dimension (T1) (wherein particle direction of the tangential dimension perpendicular to cellulosic material)； Both third will be put into the regulation room for maintaining 65 ± 3% relative humidity and 21 ± 3 DEG C through processing thin slice and control thin slice In, until realizing constant weight；4th, 30 points will be both immersed in 24 ± 3 DEG C of distilled water through processing thin slice and control thin slice Clock；With the 4th, after being removed in water, tangential dimension of the measurement through processing thin slice with both control thin slices, to obtain rear tangential ruler Very little (T2)。
DoN refers to the degree of neutralization of carboxylic acid functional in polymer.
The Percent expansion (S) of each independent thin slice (through both processing thin slice and control thin slice) calculates as follows:
In each example of this paper, the Percent expansion for compareing thin slice is 3.0%.
Water repellent efficiency (Water-repellency efficiency；WRE) for determining inorganic agent to through handling cellulose The validity of material increase water repellent characteristic.WRE is calculated as:
S1Refer to the Percent expansion of untreated thin slice；S2Refer to the Percent expansion of treated thin slice.According to E4-11, for most of outdoor applications, 75% minimum WRE is preferred.
Following instance show the disclosure in some terms, but the scope of the present invention be not limited to following instance.
Material
Absorb the thermoplastic polymer aqueous dispersions .Maincote of epoxy resinTMAEH-10 is commercially available styrene-acrylonitrile copolymer The mix moisture dispersion liquid (being purchased from Dow Chemical) of yogurt glue and 30% bisphenol A epoxide resin.MaincoteTM AEH-10 Solid content be 53%, provided epoxide equivalent (Epoxy Equivalent weight；It EEW) is 1180, minimum film forming Temperature (minimum film formation temperature；It MFFT) is about 13 DEG C, and viscosity is less than 400cP.By adding Enter water and dispersion liquid is diluted to 30 solid %.This dispersion liquid is hereinafter referred to as " EITP ".
OUDRASperseTMWB 3001 is the aqueous dispersions of commercially available liquid epoxies, is made in the case where not adding solvent It makes, has characteristics that solid content: 64%；Epoxide equivalent Wt:310g/eq；MFFT: < 0；Viscosity: 3800CP；Density: 1.10kg/L；Appearance: milky.Solid content is adjusted to 40% by addition water.This dispersion liquid is hereinafter referred to as " WB 3001”。
Polyetheramine 1.Jeffamine M-1000 is the commercial product of Heng Ziman, and is polyether monoamine, and molecular weight is about It is 1000, and PO/EO molar ratio is 3/19.Material is diluted to 30 weight percent with water.This dispersion liquid is hereinafter referred to as “PEA 1”。
Polyetheramine 2.Jeffamine ED-900 is the commercial product of Heng Ziman, and is polyether diamine, and molecular weight is about It is 900, and EO/PO molar ratio is 12.5/6.0.Material is diluted to 30 weight percent with water.This dispersion liquid is hereinafter referred to as “PEA 2”。
Treating of wood provides seven pieces of yellow pine blocks (4cm × 2cm × 0.5cm), and uses ring in the Parr reactor vacuumized Six blocks are pushed into half an hour respectively, suck 80ml PEA 1 or PEA 2 as defined in Table 1 later.It under a nitrogen will reaction Device is forced into 150psi and is kept for 60 minutes.Then the wooden unit of dipping is placed in 60 DEG C of air -oven 48 hours.
Retain two from this program through process block and (one is handled with PEA 1, and one at PEA 2 as control Reason).Remaining four pass through following post-processing through handling each personal EITP dispersion liquid of wooden unit: vacuumizing Parr reactor first It is middle that wooden unit is pressed down on into half an hour with ring, 80ml EITP dispersion liquid is sucked later.Reactor is forced under a nitrogen 150psi is simultaneously kept for 60 minutes.Then the wooden unit of dipping is placed in 60 DEG C of air -oven 48 hours.
Leaching test is carried out by washing wooden unit at 35 DEG C with deionized water, continues 8 hours, and then at 60 DEG C It is dried overnight in baking oven.Then the dimensional stability of timber is dried according to AWPAS E4-11 program, the results are shown in Table 1.
It is as shown in the table, has been initially provided of good waterproof efficiency (WRE) with polyetheramine processing timber, but has worked as to be gone out with water logging When, WRE is bad.However, material retains good after being gone out with water logging in the case where adding modifying agent (EITP or WB 3001) WRE.Without being bound by theory, these are the result shows that EITP or WB 3001 can be reacted with polyetheramine to make it from Water logging goes out or can be coated with timber hole to prevent polyetheramine from leaching.

Claims (9)

1. a kind of method being used to prepare through handling cellulosic material, it includes:
(a) cellulosic material is provided；
(b) the first processing scheme, it includes impregnate the cellulosic material, the polymer packet with the aqueous solution comprising polymer Containing water-soluble polyetheramine；With
(c) second processing scheme, it includes the cellulosic material is impregnated with modifying agent, the modifying agent includes aqueous dispersions, The aqueous dispersions include to contain epoxy resin.
2. according to the method described in claim 1, wherein the polyetheramine is polyether monoamine or polyether diamine.
3. according to the method described in claim 1, wherein described containing epoxy resin is epoxy resin or the heat for absorbing epoxy resin Thermoplastic polymer.
4. according to the method described in claim 1, wherein described containing diglycidyl ether that epoxy resin is bisphenol-A, Bisphenol F Two shrinks of diglycidyl ether, 1,4- butanediol diglycidyl ether, 1,6 hexanediol diglycidylether, phthalic acid Glyceride, 1,4 cyclohexane dimethanol diglycidyl ether, 1,3- cyclohexanedimethanodiglycidyl diglycidyl ether, hexahydro O-phthalic The 2-glycidyl ester or novolac resin of acid, or combinations thereof.
5. according to the method described in claim 3, wherein it is described absorb epoxy resin thermoplastic polymer formulation thermoplastic Property polymer moieties be acrylic latex.
6. according to the method described in claim 1, wherein first processing scheme and the second processing scheme carry out simultaneously.
7. according to the method described in claim 1, it, which is further included, impregnates the cellulosic material with additive.
8. according to the method described in claim 1, it, which is further included, is coated with timber with sealant.
9. according to the method described in claim 1, wherein the dipping of first processing scheme and the second processing scheme walks It is at least one of rapid to be carried out under the pressure above or below environment.
CN201780070222.2A 2016-09-30 2017-09-28 Through handling porous material Pending CN109937125A (en)

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